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Article: Cis-dihydroxylation of alkenes with oxone catalyzed by iron complexes of a macrocyclic tetraaza ligand and reaction mechanism by ESI-MS spectrometry and DFT calculations

TitleCis-dihydroxylation of alkenes with oxone catalyzed by iron complexes of a macrocyclic tetraaza ligand and reaction mechanism by ESI-MS spectrometry and DFT calculations
Authors
Issue Date2010
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html
Citation
Journal Of The American Chemical Society, 2010, v. 132 n. 38, p. 13229-13239 How to Cite?
Abstract
[FeIII(L-N4Me2)Cl2]+ (1, L-N4Me2 = N,N′-dimethyl-2,11-diaza[3.3](2,6) pyridinophane) is an active catalyst for cis-dihydroxylation of various types of alkenes with oxone at room temperature using limiting amounts of alkene substrates. In the presence of 0.7 or 3.5 mol % of 1, reactions of electron-rich alkenes, including cyclooctene, styrenes, and linear alkenes, with oxone (2 equiv) for 5 min resulted in up to >99% substrate conversion and afforded cis-diol products in up to 67% yield, with cis-diol/epoxide molar ratio of up to 16.8:1. For electron-deficient alkenes including α,β-unsaturated esters and α,β-unsaturated ketones, their reactions with oxone (2 equiv) catalyzed by 1 (3.5 mol %) for 5 min afforded cis-diols in up to 99% yield with up to >99% substrate conversion. A large-scale cis-dihydroxylation of methyl cinnamate (9.7 g) with oxone (1 equiv) afforded the cis-diol product (8.4 g) in 84% yield with 85% substrate conversion. After catalysis, the L-N4Me2 ligand released due to demetalation can be reused to react with newly added Fe(ClO4)2•4H2O to generate an iron catalyst in situ, which could be used to restart the catalytic alkene cis-dihydroxylation. Mechanistic studies by ESI-MS, isotope labeling studies, and DFT calculations on the 1-catalyzed cis-dihydroxylation of dimethyl fumarate with oxone reveal possible involvement of cis-HO-Fe V O and/or cis-O FeV O species in the reaction; the cis-dihydroxylation reactions involving cis-HO-FeV O and cis-O FeV O species both proceed by a concerted but highly asynchronous mechanism, with that involving cis-HO-FeV O being more favorable due to a smaller activation barrier. © 2010 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/134389
ISSN
2013 Impact Factor: 11.444
ISI Accession Number ID
Funding AgencyGrant Number
The University of Hong Kong
University Grants Council of HKSARAoE 10/01P
Hong Kong Research Grants CouncilHKU 1/CRF/08
HKU 7007/08P
Funding Information:

This work was supported by The University of Hong Kong (University Development Fund), the University Grants Council of HKSAR (the Area of Excellence Scheme: AoE 10/01P), and the Hong Kong Research Grants Council (HKU 1/CRF/08, HKU 7007/08P). We are grateful to Dr. Nianyong Zhu for assistance in solving the X-ray crystal structures of 1 center dot FeCl<INF>4</INF> and 1 center dot ClO<INF>4</INF>center dot MeCN.

References

 

DC FieldValueLanguage
dc.contributor.authorChow, TWSen_HK
dc.contributor.authorWong, ELMen_HK
dc.contributor.authorGuo, Zen_HK
dc.contributor.authorLiu, Yen_HK
dc.contributor.authorHuang, JSen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2011-06-17T09:18:54Z-
dc.date.available2011-06-17T09:18:54Z-
dc.date.issued2010en_HK
dc.identifier.citationJournal Of The American Chemical Society, 2010, v. 132 n. 38, p. 13229-13239en_HK
dc.identifier.issn0002-7863en_HK
dc.identifier.urihttp://hdl.handle.net/10722/134389-
dc.description.abstract[FeIII(L-N4Me2)Cl2]+ (1, L-N4Me2 = N,N′-dimethyl-2,11-diaza[3.3](2,6) pyridinophane) is an active catalyst for cis-dihydroxylation of various types of alkenes with oxone at room temperature using limiting amounts of alkene substrates. In the presence of 0.7 or 3.5 mol % of 1, reactions of electron-rich alkenes, including cyclooctene, styrenes, and linear alkenes, with oxone (2 equiv) for 5 min resulted in up to >99% substrate conversion and afforded cis-diol products in up to 67% yield, with cis-diol/epoxide molar ratio of up to 16.8:1. For electron-deficient alkenes including α,β-unsaturated esters and α,β-unsaturated ketones, their reactions with oxone (2 equiv) catalyzed by 1 (3.5 mol %) for 5 min afforded cis-diols in up to 99% yield with up to >99% substrate conversion. A large-scale cis-dihydroxylation of methyl cinnamate (9.7 g) with oxone (1 equiv) afforded the cis-diol product (8.4 g) in 84% yield with 85% substrate conversion. After catalysis, the L-N4Me2 ligand released due to demetalation can be reused to react with newly added Fe(ClO4)2•4H2O to generate an iron catalyst in situ, which could be used to restart the catalytic alkene cis-dihydroxylation. Mechanistic studies by ESI-MS, isotope labeling studies, and DFT calculations on the 1-catalyzed cis-dihydroxylation of dimethyl fumarate with oxone reveal possible involvement of cis-HO-Fe V O and/or cis-O FeV O species in the reaction; the cis-dihydroxylation reactions involving cis-HO-FeV O and cis-O FeV O species both proceed by a concerted but highly asynchronous mechanism, with that involving cis-HO-FeV O being more favorable due to a smaller activation barrier. © 2010 American Chemical Society.en_HK
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.htmlen_HK
dc.relation.ispartofJournal of the American Chemical Societyen_HK
dc.subject.meshAlkenes - chemistry-
dc.subject.meshAza Compounds - chemistry-
dc.subject.meshMacrocyclic Compounds - chemistry-
dc.subject.meshSpectrometry, Mass, Electrospray Ionization - methods-
dc.subject.meshSulfuric Acids - chemistry-
dc.titleCis-dihydroxylation of alkenes with oxone catalyzed by iron complexes of a macrocyclic tetraaza ligand and reaction mechanism by ESI-MS spectrometry and DFT calculationsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0002-7863&volume=132&issue=38&spage=13229&epage=13239&date=2010&atitle=cis-dihydroxylation+of+alkenes+with+oxone+catalyzed+by+iron+complexes+of+a+macrocyclic+tetraaza+ligand+and+reaction+mechanism+by+ESI-MS+spectrometry+and+DFT+calculations-
dc.identifier.emailWong, ELM:wongella@hku.hken_HK
dc.identifier.emailLiu, Y:lyg100@hku.hken_HK
dc.identifier.emailHuang, JS:jshuang@hkucc.hku.hken_HK
dc.identifier.emailChe, CM:cmche@hku.hken_HK
dc.identifier.authorityWong, ELM=rp00807en_HK
dc.identifier.authorityLiu, Y=rp00749en_HK
dc.identifier.authorityHuang, JS=rp00709en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ja100967gen_HK
dc.identifier.pmid20812697en_HK
dc.identifier.scopuseid_2-s2.0-77957121071en_HK
dc.identifier.hkuros185855en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-77957121071&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume132en_HK
dc.identifier.issue38en_HK
dc.identifier.spage13229en_HK
dc.identifier.epage13239en_HK
dc.identifier.eissn1520-5126-
dc.identifier.isiWOS:000282304000048-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridChow, TWS=37030673200en_HK
dc.identifier.scopusauthoridWong, ELM=8944839700en_HK
dc.identifier.scopusauthoridGuo, Z=36554069300en_HK
dc.identifier.scopusauthoridLiu, Y=8225912600en_HK
dc.identifier.scopusauthoridHuang, JS=7407192639en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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